Mixed acid anhydrides and process for production of same



Patented Aug. 11, 1953 MDKED ACID DRIDES AND PRQQESS IRQDILCTION OF SAME liiohard 'wl etstoil Orinda, Calif., assignor to Shell-Development'fiompany, Emeryville, Califi, e ee r iie efin le No Dl-awjng. Application June 19, 1951,

' ser i a l No. 232,481

1-7 Claims. (01. 260-461) This inventi n re a tea met o for themesaration of ,miired'aoid ,anhydrides" and t par ic lar y e te t a meth d .f r the-preparation ,off such mixed acid anhydrides wherein one o the a id esidu s 1 wi sw m is ie ved from a phosphoric acid of the class consistin of ph ri acid and 'thiqn qsa er iaei a a second acyl radical is derived fIfQI IIQ, dissimilar acid. Still morepartiqularly, t e inventiq jr lates to a method fo the ,p oduet en o mixe a anhvdride f o pho i ac any ac fu tio s of th hosphori a id tha are no combined in ,arihydrid linkage being combined in este n se ,an ,d ss m a acids, p cular y carboxylic acids. some of the products of'the invention are novel types o compounds; a still further aspe t o he inventio re ates t ertain of these novel comp'ounds and .types of. compounds as new compositionsof matter.

here hasbee 'eported m ho or th preparation of the mixed acid anhydride of dibenzyl phosphoric a id and ace ac d by ea tion beween s l e he zy phos hate an ,aeetyl chloride, silver, chloride being formed as a byproduct. A ou appa entl adeq te for lab a y purp ses t e method ohas'l ttlevalue for large scale preparation due to "the difficulty ofv'prepar n the si ve d henzyl phosphat and because'of th eost o theame app rently more convenient method for the paration of th xed ac danhydrid o d lbleii ty phosp aeidand ace i aqid'w asa s ih en epor ed elvin trea m n \Q .dibenzy .RIlQSbhQ ic" ac d v'vl t 'k te e- 'lnth s'ea a s h'w vent ei re aration of vthelnecessaryintermediate} narr ely,;the d h nzyl pho pha e i rou esom .i fl stly. Eu t e more. o -pra tica pu poses the, ied is st i t d t the ,prepa flati 'p lth ae tyl derivative, since .of the various keter'ies, ketene ,is the on y one th t .n h prepared ead ly, on large scale and at reasonable oo'st.

' ficcordingto the present invention, therg'now s provid d a n w a d,.e f ti ms hddfio t prepa a i 1 ,mix d a id nhydlf de er v d from phosphoric acid and dissiinilariacidsl rnethod ,of the present ihvention has; been ,found t 'bea aptablet h pro u tio io des r 'pmcluet inseod y e d Qa deonvers, .L t a sb is e method having wide applicability to the prepa'ra tio'riofrnixedacid anhydrides ofthe ge'neral class hereinbefore' and hereinaftermore full defiiied. In n any cases, the-starting' nateriallsthat arm equired in thernethod ofthe present invention-can be obtained or prepared at-1oW-cos t, and iri a number ofcases'the startingmaterialsarealready commercially available in quantity. The preparation of costly intermediates; such as the silver compounds employed in "the prior art processes, also is avoided by the procedure that is provided by the present invention. Because of the relative simplicity of the required procedure, the method of the present invention is vvell adapted to efiicient application ona large scale. These and other advantages ofthe method of the present invention will be brought forth more fully in winezmqr detaile -di closureslq hegi ve it pn. 6

I has W nd overed nl eeordanc zw thithis ie s i ientha a r e t le PhQD Qri ew en r a d-wit -aqi sq s i simi dammbine thsuch1a ei1 a des-wi he re rma Y h dride lia sage e n a sfi d b J ste li a e and th stewe -We tfieiqll isitheeqy ereu o the a i hal d reactant 11 1 i been d s ver tha h a t ia 1 phosph heate i t :a e t mnera eW h an qu mq r amount or a bqsvli a id hal de he tw mate ia s rea 0 swa w oth rs ir m des r heimi e e id-aa d lqf t aqp res onsii s.flialkylhhosweeni ad an the a b xvli aci and, as nyproque h vyr halid tha corresponds to the hale en e th 1 ar19 x li acid zha ide and the alk 29 ir s he' t e lsy phosphate. A $11 e' xample f the rea t on :i rovided {by the e t oni t i hy os h te@w-a 1flim thi1care X z eh qride to ter th mi ed aci nhydride o d me h l e tmi wil andfl e ylphosphoric flhere mays beformed in lesser amounts, depending pon the"particu1ai" reaction co iiditions, mired aoid'anhydrids 'i'n which-two, or" vh an three of the valelicies or the pho'sphoryl radical are satisfied 1 by the acyl group of the dissimilar oXy-acid, thefdrmation of-these {more eeiiimx mixed-acid anhydrides presiumably 'pr d gia cording to the followih'g"illustrative equations that are based upon the specific example used above:

The method of the present invention, which invention is considered to be generic to the reaction of triesters, or neutral esters of phosphoric acid with acid halides of dissimilar acids to produce one or more mixed acid anhydrides containing an acyl group of each of the reactants, and to the process for effecting the same, is carried out by heating a mixture essentially comprising the phosphoric acid ester and the acid halide of the dissimilar acid at an elevated temperature that is conducive to the reaction but below a temperature at which decomposition of the reactants or products occurs. The reaction is flexible in the sense that the two reactants may be employed in various proportions relative to each other, the optimum proportions being determined in part by the particular product that is to be prepared and in part by the associated conditions under which the process is executed. The reaction is capable of being carried out non-catalytically, i. e., without added catalysts. Appropriate catalysts can be used, however, to increase the rate of reaction. Solvents, or diluents may be included in the reaction mixture. The reaction i favored by withdrawing from the reaction mixture, or otherwise separating from the reaction mixture, either continuously or intermittently, the organic halide that is derived from the ester radical or radicals of the phosphoric acid ester and the halogen of the acid halide. The reaction may be carried out under applied pressure. After the reaction has been effected, the required time depending upon the conditions and reactants used, recovery of product can be carried out by conventional methods, such as by fractional distillation, by treatment with selective solvents, by adsorption, etc. If desired, depending upon the intended use for the product, separation of the product from the reaction mixture may without departure from the invention be dispensed with and the crude mixture used either in its entirety or after removal only of any solvent that may be present, catalysts, unconsumed reactants, etc.

In a preferred method for carrying out the process of the invention, the triester of phosphoric acid is heated in admixture with the selected halide of the dissimilar acid, for exam ple, a carboxylic acid chloride, at a temperature within the range of from about 75 C. to about 250 C., a preferred range being from about C. to about C. When the desired mixed acid anhydride contains but one anhydro grouping, that is, but two acyl groups-one derived from the phosphoric acid and the other from the dissimilar acid-the amount of the acid halide reactant desirably is limited to an amount within the range of from about 0.1 to about 1.5 moles, preferably from about 0.2 to about 1 mole, per mole of the phosphoric acid ester. When the desired mixed acid anhydride contains two or even three anhydro groupings, i. e., when it contains two or even three acyl groups of the dissimilar acid, proportionally larger amounts of the acid halide reactant are employed, such as up to about 5, 10, 15 or even more moles per mole of the phosphoric acid ester. Useful products are obtained with especial efiiciency when there is employed from about 0.2 to about 5 moles of the acid halide reactant per mole of the phosphoric acid ester. The process may be carried out with the aid of superatmospheric pressures, as when one or both of the reactants otherwise would volatilize excessively from the reaction mixture. Alternatively, a volatile reactant may be added to the reaction mixture portionwise during the heating period, although the use of pressure is generally a preferable method of operation when the reaction temperature is above the atmospheric boiling point of a reactant. As the reaction commences and progresses, the organic halide that is formed as by-product of the reaction desirably is withdrawn from the reaction mixture either continuously or intermittently as it is formed. When the halogen ester has an appropriately low boiling point, it may be volatilized and allowed to escape from the reaction mixture as it forms. In other cases, it may be separated from the reaction mixture either intermittently or continuously, as by fractionation of the mixture or of a portion thereof, or by other appropriate methods, the choice of which will depend upon the particular system that is involved. The course of the reaction can be followed conveniently by measurement of the amount of evolved organic halide, by determination of the amount of acid anhydride present in the mixture, or by other appropriate methods. When the reaction has gone to substantial completion, generally after from about 1 to about 10 hours elapsed reaction time, or at any desired earlier time, the heating is discontinued and the resulting mixture worked up according to any suitable procedure for recovering the product or products in the desired state of purity. As indicated hereinbefore, distillation,

treatment with selective solvents, and adsorption are among the methods that can be used.

As catalysts for the reaction there can be employed acid-acting substances as well as basicacting substances. Acids, such as mineral acids and the various organic acids, can be used as suitable acid-acting substances, examples thereof including, among others, sulfuric, hydrochloric, hydrobromic, phosphoric, nitric, arsenic, boric, phosphorous, pyrophosphoric, and such organic acids as salicic, chloracetic, p-toluenesulfonic, oxalic, acetic, formic, benzenesulfonic, and chlorobenzoic acids. The strong acids, having dissociation constants in water greater than abou 1 are preferred. Bases. other than hose hat ombin w th acid hal d s to form alt or amides parti ula ly tertiary aminesar suitable as basic-acting substances, examples of such basic catalysts including, without being limited to, triethylamine, N,N-dimethylcyclohexylamine, tri-isobutylamine, N,N-dimethylaniline, N-ethylpiperidine, pyridine, and benzyltrimethylammonium and other quaternary ammonium salts, e. g., acetates, nitrates, chlorides, etc. The reaction is carried out under substantially anhydrous conditions. The catalyst, if one is employed, conveniently is one that is sufficiently soluble in the anhydrous reaction mixture to give the requisite concentration therein, a concentration of the catalyst of from about 0.001% to about 5% or more (Weight basis) generally serving .to providea pronounced acceleratins action in th action.

The following examples will illustrate certain of the numerousspecific embodiments of the invention. It will be understood that the examples ar presented with the intent ofillustrating and not of limiting the invention, and that various modifications can be resorted to without departmg from the letter and spirit of the invention as defined in the appended claims.

Example I There were mixed 649 grams of triethyl phosa phate and 334 grams of benzoyl chloride in a glass lined reaction vessel equipped with a watercoo'led reflux condenser. The upper end of the condenser opened to the atmosphere through a cold-trap chilled with acetone-solid C02. The mixture was 'heated at 130 C. to 163 C. for '2 hours. During this time ethyl chloride was evolved and collected in the cold-trap, in the amount of 135 grams. The reaction mixture then was stripped of low-boiling constituents by distil lation to a maximum kettle temperature of 157 C. under 1 to 2 mm. mercury pressure. The non-volatilized portion was dissolved in benzene, the solution was treated with Duolite A-2 resin (an anion-exchange synthetic resin produced commercially by the Chemical Process Company, San Francisco), and the filtrate was fractionally distilled. The fraction distilling between 130 C. and 149 C. under 1 to 2 mm. mercury pressure was collected separately and identified .as the mixed anhydride of benzoic acid and diethyl phosphoric acid, having the structure Anhydride value (equivalents of anhydride per 100 grams): Found, 0.369; calculated,0.388. Refractive index (n 20/D): 1.5000.

6? each run the reactants were employed in the ratio of 1 mole triethyl phosphateand 0.5 mole benzoyl chloride. The reaction temperature was 148 C. In each run the extent of reaction was determined by measurement .ofzthe amount of ethyl chloride evolved. The following results were observed:

, :itste tao Reaction Amount, Mter'lfiO Eercent f Minutes (Percent of Theory) Catalyst triethylamine p-toluegesulfonicacid none ,A mixture of equimolar amounts .of "benzoyl anhydride of benzoic acid and diethyl phosphoric acid to be the chief product, as follows: Found, 11.1% P; 52.7% C; 5.4% H. Calculated fort-he mixed anhydride of benzoic acid and diethyl phosphoric acid, P; 51.1% C; 558% Example If A mixture of 92.1z ramsofphenylacetyl chloride and 218 grams of triethyl phosphate was heated at C. to C. .for 1.4 hours. .Ethyl chloride was evolved from the reaction mixture as the reaction progressedinan amount totalling 83.5% of theory. The resulting mixture then was stripped of lower low-boiling constituents by heating to a final kettle temperature .of 155 C. under 2 mm. mercury pressure. The remaining portion of the mixture, amounting to '124-grams,

contained the mixed anhydride of phenylace'tic acid and diethyl phosphoric acid along with lesser amounts of the mixed ,an'hydrides of phenylacetic acid and ethyl phosphoricacid and phosphoric acid. The anhydride value of the mixture was found to be 0.266 equivalent of anhydride per 100 grams compared to the calculated value of 0.367

Example VI O CaHsC CHaO O omo Example VII A mixture of 70.3 grams of benzoyl chloride and 199 grams of tributyl phosphate was heated at 150 C. to 185 C. for 3 hours, n-butyl chloride being evolved as the reaction progressed. The amount of n-butyl chloride liberated in this time amounted to 68% of theory. The resulting mixture then was fractionally distilled, a fraction of 46 grams being separated from the distillate at 120 C. to 142" C. under a pressureof 1 to 2 mm. mercury. A higher-boiling fraction of 104 grams was allowed to remain in the still kettle. The fraction of the distillate contained the mixed anhydride of benzoic acid and dibutyl phosphoric acid. The undistilled fraction contained, in addition to this mixed anhydride, the anhydrides of benzoic acid and butyl phosphoric acid and phosphoric acid. The structures of these three anhydrides can be represented by the following formulas:

CaHsO In a manner similar to that illustrated in the foregoing examples there can be prepared other 8 mixed acid anhydrides derived from aromatic carbocyclic monocarboxylic acids and phosphoric acid, having structures that can be represented by the general formula:

in which signifies the acyl residue of an aromatic carbocyclic monocarboxylic acid, OR" signifies the residue of an aliphatic monohydric alcohol denoted by R"OH, m signifies a whole number having a value not less than 1 nor greater than 3, and n=3m. Additional illustrative mixed acid anhydrides that have structures corresponding to this formula and that can be similarly prepared include, among others, the following: mixed acid anhydride of p-toluic acid and dibutyl phosphoric acid; mixed acid anhydride of, p-nitrobenzoic acid and monoisopropyl phos-' phoric acid; mixed acid anhydride of p-chlorom-methylbenzoic acid and di-Z-cyanoethyl phosphoric acid; mixed acid anhydride of 2,4,5-trichlorophenylacetic acid and dioctyl phosphoric acid; mixed acid anhydride of o-carbethoxybenzoic acid and di-2-isothiocyanoethy1 phosphoric acid; mixed acid anhydride of p-phenylbenzoic acid and bis(3-methoxypropyl) phosphoric acid; mixed acid anhydride of p-t-butylbenzoic acid and diethyl phosphoric acid; mixed acid anhydride of p-t-butylbenzoic acid and diallyl phosphoric acid; mixed acid anhydride of p-t-butylbenzoi-c acid and mono(2-ethoxyethyDphosphoric acid; mixed acid anhydride of of p-t-octylbenzoic acid and bis(3,5,5-trimethylhexyl) phosphoric acid; mixed acid anhydride of benzoic acid and dilauryl phosphoric acid; mixed acid anhydride of benzoic acid and 2-chloroally1 phosphoric acid; mixed acid anhydride o-f p-allylbenzoic acid and diethy1 phosphoric acid; mixed acid anhydride of p-dodecylilar compounds that contain but the acyl rad--v ical of a lower fatty acid in place of the acyl radical of the aromatic acid. In the following tests, infested plants were sprayed with solutions prepared by dissolving products prepared in the foregoing examples in a diluent spray oil and the results were compared with the results of similar tests in which the mixed acid anhydrides of acetic acid and diethyl phosphoric acid (prepared in Example VIII) and acetic acid and dibutyl phosphoric acid (prepared in Example IX), respectively, were employed. All of the tests were run under controlled conditions that differed only with respect to the prodnot being tested and the concentration thereof in the spray oil. Thus, the same volume of spray and the same conditions of spraying were.

637% Hi; anhydride value; 0.51.

9 used" in each test. The results shown in" the following table were observed:

To 98v grams of triethyl phosphate at 120C. to 150 C. there were added po-rtionwise-over a period of. 11 hours 39 grams of'acetyl chloride, ethyl chloride being evolved from the mixture as the reaction progressed. The resulting mixture then was rapidly distilled from a Claisen flask. and

the distillate was fractionated by redistill'ation. Themixed acid anhydride of acetic acid and 'diethyl phosphoric'acid having the structure was recovere'd as'the fraction. distilling between 9.1.3 C. and 9.8. C; under a pressure of 3 mm. mercury. Analyses: Found, 36.8% C; 6.7%. H; anhydride value, 0.44; Calculated, 36.7 C; Higher boiling products ofthe'reaction' were indicated to contain the mixed acid anhydrides of acetic acid and ethyl phosphoric acid and phosphoric acid, having the respective structures canton? and onto".

CHa-O- Example IX 10 mixed anhydride of propionic acid and diethyl phosphoric acid, having thestr-ucture OHiCHiO 0,1150 o 021350 0 was recovered as the fraction distilling between 71C. and 74C. under a pressure of' l to 2mm. mercury. Analyses: Found, 40.2% C; 7.5% H; anhydride value, 0.43. Calculated, 40.0% C; 7.2% H; anhydride value, 0.48.

Example X A mixture of 1305 grams of furoyl chloride and 364" gramsof triethyl phosphate was heated at 143 C. to 156 C. for 7.5 hours, ethyl chloride being evolved from the mixture and collected in a cold trap as in the preceding. examples'; When the reactionwas discontinuedjthe amount of ethyl chloride that had been collected amounted to. 76% of theory. The reaction mixture then was fractionally distilled under a pressure of 2 to 3" mm. mercury. There were obtained" 137 grams of product distilling'betwe'en 140 C. and 152 C." The collected product; the

mixed anhydride of furoi'c. acid and 'diethylphosphoric acid, was found to have. the following elemental analyses; Found, 45.3% C; 5.7% H; 11.5% P. Calculated, 43.55% C;v 5.28% H; 12.48% P. 'Ihe'structureof'the mixedanhydride of. furoic acid and diethylphosphorici acid is" CzHsO Example XI To 218 grams of triethyl phosphate there were added 64 grams of dimethylcarbamyl chloride and the mixture was heated at 146 C. to 152 C. for 1.1 hours, ethyl chloride. being; evolved as the reaction progressed. The reaction mixture then was heated under 2 mm. mercury pressure to 135 C. in order to remove any lower boiling materials that were present. The resulting, mixture: was found to, contain; as the principal product; the mixed acid anhydride. of dimethylcarbamic acid and diethyl phosphoric acid with lesser amounts of the mixed acid anhydrides of dimethylcarbamic acid and ethyl phosphoric acid and phosphoric acid, respectively. Thestructures or. these. anhydrides can .bev representedby the following structurarformulas:

Tests of the product showed it to have a high insecticidal activity when sprayed as a 0.1% solutionin a diluent spray oil upon infested plants.

Further tests showed the product to have the desirable property of activity as a systemic poison, that is, when applied to the soil in the vicinity of plants it was absorbed by the plant 'and rendered the plant as a whole toxic to 1n- 'sects.

Example XII 122 C. under 4 millimeters mercury pressure followed by further heating in a molecular still at 56 C. under 0.035 millimeter mercury pressure. The residue then was molecularly distilled at 101 C. under 10" millimeter mercury pressure. There were obtained 75 grams of a yellow distillate (n 20/D 1.5068) that by analysis was a mixture of the mixed acid anhydrides of diethylthiocarbamic acid and diethyl phosphoric acid and ethyl hosphoric acid.

The mixed acid anhydrides prepared in Examples XI and XII are illustrative members of a novel class of insecticidally active mixed acid anhydrides that can be represented by the structural formula in which the group is the amino residue of an organic primary or secondary amine represented by a the group -OR' signifies the residue of an alcohol or phenol denoted by ROH, m signifies a whole number having a value not less than 1 nor greater than 3, X represents a chalcogen element having an atomic number that is an integral multiple of 8 (i. e., oxygen or sulfur), and n=3m. Of this group, those wherein each X represents oxygen are of particular value and are preferred. The radical denoted by each R. is preferably an alkyl, aryl, or an alkaryl radical. The group represented by may comprise an N-heterocyclic ring that includes the nitrogen atom, e. g., piperidino, pyrollidino, morpholino, or alkyl substitution products of the same. Additional illustrative compounds The mixture was then freed of this group, which can be prepared by the procedure of this invention include, among others: mixed acid anhydride of piperidine-N-carboxylic acid and butyl phosphoric acid; mixed acid anhydride of diisopropylcarbamic acid and diphenethyl phosphate; mixed acid anhydride of N-methylphenylcarbamic acid and 2-ethoxyethyl phosphoric acid; mixed acid anhydride of bis(1,3-dimethylbutyl) carbamic acid and dioctyl phosphoric acid; mixed acid anhydride of N- isopropyloctylcarbamic acid and bis(2-chloroethyl) phosphoric acid; mixed acid anhydride of bis(p-chlorophenyl)carbamic acid and dimethyl phosphoric acid; mixed acid anhydride of diisopropylcarbamic acid and diallyl phosphoric acid; mixed acid anhydride of diisopropylcarbamic acid and monoallyl phosphoric acid; mixed acid anhydride of 2-mcthylpiperidine-N-carboxylic acid and dioctyl phosphoric acid; mixed acid anhydride of l-chlorobutyl N-(S-chloroallyDisopropylcarbamic acid and diethyl phosphoric acid; mixed acid anhydride of dimethyl carbamic acid and butyl phosphoric acid; mixed acid anhydride of bis(1,3-dimethylbutyl)carbamic acid and dilauryl phosphoric acid; mixed acid anhydride of ditetrahydrofurfurylcarbamic acid and dipropyl phosphoric acid; mixed acid anhydride of dibutylcarbamic acid and dibutyl phosphoric acid; mixed acid anhydride of dicyclohexylcarbamic acid and dimethylphosphoric acid; mixed acid anhydride of dimethylthiocarbamic acid and ethyl phosphoric acid; mixed acid anhydride of diisopropylthiocarbamic acid and dibutyl phos phoric acid; mixed acid anhydride of diethylthiocarbamic acid and p-nitrophenyl phosphoric acid; mixed acid anhydride of diphenylthiocarbamic acid and di-2-chloroethyl phosphate; and mixed acid anhydride of dioctylthiocarbamic acid and propyl phosphoric acid.

Still further specific embodiments of the present invention are illustrated in the following examples.

Example XIII A mixture of 98.5 grams of methanesulfonyl chloride and 365 grams of triethyl phosphate was heated at C. to 148 C. for 3.25 hours. During this time ethyl chloride was evolved from the reaction mixture in an amount corresponding to 64.5% of theory. The mixture then was stripped of low-boiling materials by heating under about 1 mm. mercury pressure to about 60 C. leaving an undistilled fraction containing the mixed anhydride of methanesulfonic acid and diethyl phosphoric acid. The structure of this mixed acid anhydride can be represented by the formula Example XIV Chloroacetyl chloride and triethyl phosphate were reacted according to the method illustrated in the preceding two examples to produce a mixture containing the mixed acid anhydride of chloroacetic acid and diethyl phosphoric acid. The structure of this mixed anhydride can be represented by the formula As shown by: the foregoing, examples-,. the method of the present invention-can be. applied to the synthesis of. a wide variety of mixed acid anhydrides in which the phosphoryl group is at.- tached directly. through: oxygen to atleast one acyl group of an organic oxy-acid of-a dissimilar element, in which:any valencies of thephosphoryl group that. are not thus satisfied are, united through.- oxygen to'an ester residue, e; g,,.to-the residue of an alcohol or a phenol. The structure of the mixed acidanhydrides that can be produced by the process of: this invention can: be represented by the general; structural formula in which R represents-theacyl group-of the acid that is referred to hereinas the dissimilar' acid, R. represents-the ester residueof the phosphoric acid ester used as reactant, X represents oxygen or sulfur, 9: represents a whole number. not less than 1. and not greater than 3, andy, represents a: whole number such. that r+y always equals-3. Typical acid halides that can be reacted with triesters-of phosphoric acidaccording tothe invention to produce such mixed acid anhydrides include acid halides of unsubstitutedfatty acids, such asacetyl chloride, propionyl chloridabutyryl. chloride, valeryl chloride, caproyl chloride, caprylyl chloride, pelargonyl chloride, capryl chloride, lauryl chloride, myristyl chloride, palmityl chloride, stearyl chloride, and. their homologs and various: branched-chain isomers; acid halides of unsaturated aliphatic. acids, such as acrylyl chloride, methacrylyl. chloride, crotonyl chloride, hydrosorbyl chloride, tetrolyl chloride, oleyl chloride, Iinoleyl chloride, and 2,4-pentadienoyl chloride; acid halides of aromaticaci-ds, such as benzoyl chloride, toluyl chloride, naphthoyl chloride, cinnamylchloride, biphenylacetyl chloride, p-chloroformylbenzoic acid, terephthal'oyl chloride, p-t-butylbenzoyl chloride,

methyl-p-t-butylbenzoyl chloride, and p-octadecylbenzoyl chloride; acid halides of. carbonic acid and of functional derivatives of carbonic acid, such as phosgene, carbamyl chloride; methylcarbamyl chloride, diethylcarbamyl" chloride, ethyl" chloroformate; propyl chloroformate',. noctyl chloroformate, phenyl' chloroformate, N'-

piperidinecarbonyl chloride, bis(l",3"-dimethylbutyDcarbamyl chloride, diallyl'carbarnyl chloride; N-plienylmethylcarbamyl chloride, and cyclohexyl chloroformate; acid" halides of cycleaIipha-tic acids, such as. cyclop'entanecarbonyl chloride, dimethylcyclopentanecarbonyl chloride,

and cyclohexanecarbonyl chloride; and acidihalides of polycarboxylic acids, such as ii-chlor 'formylpropionic" acid; adipyl' chloride, succinyl chloride, phth-alyl. chloride; tetrachloro-2,- errdomethylenetetrahydrophthaiyl chloride, and glut'aryl chloride. Acid halidesof other organic acids than carboxylicacids can' be employe'diin accordance with the process of the generidinventionto produce mixed-acid" anhydrides as .hereinchloride and p-nitrophenylthioacetyl" chloride,

and acid halides of organic sulfonic and sulfinic acids, such as methane sulfonyl chloride, benzene fsulfonyi' chloride, II-butanesulfonyL chloride, and

benzenesulfi'nyl chloride; and the seleno, the

tellurm, the: borono, the; silica,. and the. arseno analogs of such sulfonicand sulfinic-acidthalides. The: acid. halide; that. isreacted withv the. phasephor-ic acid ester: according tothe. inventionmay be defined in. the: generic. sense. as being. of the class consisting of the acid halides of oxy-acids of polyvalent oxide-forming. non metallic elements, other than-phosphorusandthe analogs of suchzoxy-acids wherein oxygen. of the acid iunction. is.- replaced by sulfur. The preferred. acid halides are those derived from the carboxylic acids. The organic. residue of the. acid halide maybe unsubstituted, e.-.g., an unsubstituted hydroca-rbon group, or itmay contain. one-or more inert substituents, such as cyano, nitro, sulfo, halogen, e.- g.,.chlorine; bromine, or fluorine, the ether group; or. ---O-- linkage, the. ester. group, or'--O--OG- linkage, the mercapto group,. or -.Silinkage, or the ketonic (C0-) group.

As tor thehalogen. of, the acid halide for reasons of availability and. cost, the acid. chloride ordinarily is used; Theprocess. of theinvention is not limited to the acid chlorides, however,.and the: corresponding, acid halides containing; other halogens, e; g:, bromine, iodine or: fluoriner can be-usedinstead. The chlorides andbromidesare preferred;

As the ester' of; phosphoric acid, there may. be employed in. accordance with the-inventions any neutral ester, or triester, of phosphoric. acid. There-also may beemployed, althoughless. desirably, corresponding esters ofthiophosphoric acid, (HOMPS. Illustrative esters are the esters of phosphoric acid and aliphatic alcohols, such. as the tri-alkyl; esters and: the substituted. tr-ialkyl esters of phosphoric acid, e.. g.,. triethyliphosphate, tris('2:-chloroethyl) phosphate, trioctyl phosphate, tris(2-ethoxyethyl). phosphatatriisobutyl? phosphate, tris.(3;5;5Ftrimethylhexyl) phosphata diethyl cyanoethyl phosphate, andmethyl diethyl. phosphate aswell as arylesters of phosphoric: acid;.suchas--tricresyl phosphate, triphenyl phosphate, diethyl-phenyl-phosphate, dinaphthyl butyl phosphate,. tris(p-methoxyphenyl) phosphate, tris(p-nitrophenyl) phosphate, and bisfp-carbethoxyphenyl) ethyl phosphate, the lower trialkyl esters beingpreferred; Illustrative esters of thiophosphoric acid include, among others, triethyl thiophosphate, trimethylthiophosphate, tripropyl thiophosphate, triphenyl thiophosphate, etc. The three ester groups of the phosphoric acid. ester may be the same or they may be dissimilar. One. ormore of the ester groups may be substituted by inert substituents, as by one or more of cyano, halogen, alkoxy, carboalkoxy, isocyano, or mercapto, or the ester groups preferably may all i be residues of unsubstituted lower aliphatic. alcohols. The process of the invention is particularly efiective for the preparation of desired mixed acid anhydrides from-neutral esters ofa'phosphoric acidiarrddower aliphatic monohydric alcohols.

The mixed acid anhydrides that are produced according to the process 'of this invention include materials that are useful as insecticides, germicides, fungicides, and like toxicants. In such uses they may. be applied. inv the form of solutions, emulsionsor suspensions in. inertrli-quid" diluents, in dustform carried. by. solidi finely-divided] car rier material, alone.- or. inconjunction with previously known. insecticides, germicides, fungicides, etc. When used...as.systemic poisons the toxicant is applied to or into the groundinthe vicinity of the. plant,, or directly onto. the. plant,, whereupon itis. absorhedby the. plantrendering the. plant. as a whole toxic to many pests. Additional uses that come into consideration for products that can be produced by the process of this invention are as additives for gasolines and other fuels for internal combustion engines, additives for 011s and greases, and intermediates in organic syntheses.

' I claim as my invention: I

1. Process for the production of a mixed acid anhydride which comprises heating dimethylcarbamyl chloride and triethyl phosphate in admixture in mole proportion of from about 0.5 1 to about 1:1 ata temperature of from about 100 C. to about 200 C. to produce a product comprising mixed acid anhydride of dimethylcarbamic acid and diethyl phosphoric acid.

2. Process for the production of a mixed acid anhydride which comprises heating dialkylcarbamyl chloride and trialkyl phosphate in admixture in mole proportion of at least about 0.1 1 at a temperature of from about 100 C. to about 250 C. to produce a product comprising mixed acid anhydride of dialkylcarbamic acid and an alkyl phosphoric acid.

3. Process for the production of a mixed acid anhydride which comprises heating a mixture comprising about one mole of a trialkyl phosphate and from about 0.1 to about 5 moles of an N-dlsubstituted carbamyl chloride at a temperature of from about 75 C. to about 250 -C. and continuing the heating until there is formed a product comprising mixed acid anhydride containing the phosphoryl group and N-disubstituted carbamyl group interconnected directly through one atom of oxy en.

4. Mixed acid anhydride of dimethylcarbamic acid and diethyl phosphoric acid.

5. Mixed acid anhydride of dialkylcarbamic acid and dialkyl phosphoric acid.

6. Mixed acid anhydride of N-disubstituted carbamic acid' and phosphoric acid having at least one but not more than two acid functions of said phosphoric acid combined in ester linkage with an aliphatic monohydric alcohol and the other acid functions of said phosphoric acid combined in the acid anhydride linkage thereof.

7. A mixed acid anhydride having a structure represented by the formula (RO P\ in which the group is the amino residue of an organic amine represented by anhydride which comprises heating benzoyl chloride and triethyl phosphate in admixture in about 200 C. to produce a product comprising mixed acid anhydride of benzoic acid and diethyl phosphoric acid.

9. Process for the production of a mixed acid anhydride which comprises heating an acid chloride of an aromatic carbocyclic monocarboxylic acid and a trialkyl phosphate in admixture in mole proportion of from about 0.1 1 to about 5 1 at a temperature of from about 75 C. to about 250 C. to produce a product comprising mixed acid anhydride of the aromatic carbocyclic monocarboxylic acid and an alkyl phosphoric acid.

10. Process for the production of a mixed acid anhydride which comprises heating an acid halide of an aromatic carbocyclic monocarboxylic acid and a triester of phosphoric acid with at least one of the class consisting of alcohols and phenols in admixture in mole proportion of at least about 0.1 1 at a temperature of from about 75 C. to about 250 C. to produce a product comprising mixed acid anhydride wherein the acyl group of said aromatic carbocyclic monocarboxylic acid is connected directly through an atom of oxygen to the phosphoryl radical.

11. Mixed acid anhydride of benzoic acid and diethyl phosphoric acid.

12. Mixed acid anhydride of benzoic acid and monoethyl phosphoric acid.

13. A mixed acid anhydride having a structurerepresented by the formula H II R oo .,.1 0R").. in which anhydride which comprises heating an aliphatic sulfonic acid chloride and a trialkyl phosphate in admixture in mole proportion of from about 0.1:1 to about 1.521 at a temperature of from about C. to about C. to produce a product comprising mixed acid anhydride of said aliphatic sulfonic acid and dialkyl phosphoric acid.

15. Process for the production of a mixed acid anhydride which comprises heating together a triester of phosphoric acid with at least one of the class consisting of alcohols and phenols and a carboxylic acid halide in mole proportion of at least about 0.1:1 at a temperature of from about 100 C. to about 175 C. V

16. Process which comprises heating a triester of a phosphoric acid of the class consisting of phosphoric acid and thiophosphoric acid with at least one of the class consisting of alcohols and phenols together with at least about 0.1 mole per mole of said triester of an acid chloride of a dissimilar acid at a temperature of from about 100 C. to about 175 C. to produce a product comprising mixed acid anhydride of said dissimilar acig and the corresponding diester of phosphoric aci 17. Process which comprises heating a triester of a phosphoric acid of the class consisting of phosphoric acid. and thiophosphoric acid with References Cited in the file of this patent at least one of the class consistir g of alcohols UNITED STATES PATENTS and phenols together Wlth a reactlve proportion of an acid halide of a dissimilar acid to produce Numbfi Name Date a mixed acid anhydride wherein the phosphoryl 5 2,478,377 Dlckey 9, 19 9 radical and the acyl group of said dissimilar acid 2,486,658 Kosolapofi 1, 949 are interconnected directly through an atom of OTHER REFERENCES oxygen.

Brooks, J. Am. Chem. 800., vol. 34, pages 492 to RICHARD R. WHETSTONE. 10 499 

